DE1794012A1 - Footage - Google Patents

Description

PATENT LAWYERS DR. E. WIEGAND DIPL-ING. W. NIEMANN 179A0

DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MDNCHEN HAMBURG

TELEPHONE, 555470 8000 MONKS 15,2Y. AUgUSt 1968

TELEGRAMMEi KARPATENT NUSSBAUMSTRASSE

W .. 13828/68 5 / Pe

Bexford Limited Brantham, Essex (England). j

Film material addendum to patent ... (Pat.Anm. P 15 44 664.7) '

The invention relates to synthetic film material and represents an improvement or modification of the invention according to the patent ... (patent application P 15 44 664.7).

The main patent relates to a method for producing a translucent polyester film material which is used for ^ Capture clear and legible pencil, ink, or colored characters using a film made of one synthetic linear polyester material on at least one surface with a solution or dispersion in a volatile medium of one or more halogen-containing phenolic substances at a temperature treated by at least 350 ° C and to the treated Surface an adherent layer or layers

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organic film-forming material, with the single layer or when using multiple layers the outermost layer of finely divided discrete particles of a translucency anchoring agent or agents.

The term "halogen-containing phenolic substance" is intended to encompass chemical compounds whose molecules contain at least one benzene ring or fused benzene ring and one or more hydroxyl groups and one or more halogen atoms which are bonded directly to carbon atoms which form a benzene or condensed benzene ring or Belong to wrestling. Examples of such halogen-containing phenolic substances are listed below: o-chlorophenol, p-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol , Pentachlorophenol, 2,4-diehlor-5-methylphenol, 2,4-dichloro-3,5-dimethylphenol, 4-chloro-2-phenylphenol, 2-benzyl-4-cilophenol, 2,2'-dichloro 4.4 ^f diphenol, 2,2'-methylene-bis - ^ - chlorophenol), 4-chloro-lnaphthol, J 5.5-dichloro-salicylic acid, 2,4-dibromophenol, 2,4,6-tribromophenol, isopropylene di- (2,5-dichlorophenol).

109831/2195 BAD ORiQiNAL

Preferably the synthetic linear polyester film is made of one made of polyethylene terephthalate formed film and is preferably one that is formed by stretching in one or two directions in the right Angle has been molecularly oriented. Such synthetic linear polyester film materials are easy on the market available.

The treatment can expediently consist in applying to the surface of the synthetic linear polyester film a solution of one or more of the halogen-containing phenolic materials indicated above in suitable volatile media which e.g. B. lower ketones, lower alcohols or chlorinated hydrocarbons, or dilute solutions of volatile bases, such as dilute ammonia, represent, any of the various well-known coating processes, for example the { dipping or application process (bead application) are used, whereupon the The film is heated for a short period of time at an elevated temperature to remove the volatile solvent and to allow the halogen-containing phenolic substance to swell the film surface to some extent.

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The presence of an intermediate layer between the treated surface of the polyester and the organic one The film-forming layer is also provided with a large number of examples of such intermediate layers in the Description of the main patent given.

In the description of the main patent it is further described that the preferred anchoring agent is silica represents that but also other anchoring means, such as. B. zinc oxide or titanium dioxide are also present can.

According to the invention, a film material is created, which can be converted into a lithographic printing plate and a backing layer of polyester film material comprising at least one surface of the polyester film material having a solution or a dispersion in one volatile medium of at least one substance, such as halogen-containing phenolic substances or chlorine-substituted substances aliphatic acids has been treated at a temperature of at least 50 ° C, and wherein to the so treated Surface adheres to an intermediate layer, such as

(a) Vinyl chloride-vinyl acetate copolymers

and partially hydrolyzed vinyl chloride-vinyl acetate copolymers,
or (b) vinylidene chloride-acrylonitrile misoh polymers and copolymers of vinylidene chloride with acrylic acid and

or (c) vinyl halogen acetates and copolymers

from vinyl haloacetates, or (d) · phenol formaldehyde, urea formaldehyde and Melamine formaldehyde resins,

or (e) cellulose nitrate and cellulose acetate butyrate, or (f) polymers of acrylic and methacrylic acids. ™ and esters and copolymers of these acids and esters with other vinyl-unsaturated monomers and wherein a hydrophilic layer which is a water-swellable organic layer is superimposed on the intermediate layer film-forming material which has been made insoluble and which contains at least one finely divided inorganic Contains filler.

The preferred polyester film base material is polyethylene terephthalate, that is biaxially oriented. . |

The halogen-containing ^! Phenolic substances can represent any one or more of those previously described. Other examples that can be used are 3-methyl-4-chlorophenol, p-chloro-o-benzylphenol and 4-chlororesorcinol. The chlorine-substituted aliphatic acid is preferably trichloroacetic acid.

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In general, the synthetic linear polyester film base is preferably made by coating with a solution of 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, 2, 'k -dichlorophenol or 5-methyl-4-chlorophenol or a binary mixture of these substances in a suitable

Treated P volatile solvent, these substances or binary mixtures representing 0.5 to 20 wt .- # of the treatment solution, and then the film is heated for 1 to 15 minutes at J> 0 ° to 120 ° C.

The intermediate layer can be applied to the polyester film from solution or dispersion in a volatile medium after the polyester film with halogen-containing phenolic substances or chlorine-substituted aliphatic Has been treated with acids, or alternatively the intermediate

Fe layer in combination with the halogen-containing substances or chlorine-substituted aliphatic acids can be applied from the same solution or dispersion.

Suitable water-swellable organic film-forming materials according to the. In the invention are: Cellulose ether, e.g. B. methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, Hydroxypropylethyl cellulose, carboxymethyl cellulose, Polyacrylamides, polyvinylpyrrolidone, sodium alglnate, natural rubber, such as B. gum arabic, polyvinyl alcohols, carbohydrate z. B. starch or dextrin, proteins, such as. B. Casein and Zein, vinyl / maleic acid polymerizate, ethylene oxide polymer

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These materials can in some cases be rendered insoluble by the application of heat or by the inclusion of a suitable wetting agent in the layer. Examples of such crosslinking agents are: urea formaldehyde, melamine formaldehyde, glyoxal and dialdehydes in general, formaldehyde, dibasic acids, e.g. B. oxalic% acid, maleic acid, tartaric acid and fumaric acid, hydrochloric acid, phosphoric acid, aluminum sulfate, iron (II) sulfate, copper sulfate, chromium salts, z. B. Ammoniumdichr.omat and chromic acid, borax, organic titanates and epoxy resins.

The preferred hydrophilic water-swellable material is polyvinyl acetate which has been hydrolyzed to the extent of 84 to 98%.

The preferred crosslinking agent for polyvinyl alcohol is a methylated melamine formaldehyde resin, with 5 to 200 wt .- ^ des polyvinyl alcohols can be used. A particularly suitable commercially available methylated melamine formaldehyde resin is operated by B.I.P. Chemicals Limited and sold under the name "B.T. J509".

Different catalysts can be used in small amounts to speed up the setting time that is necessary in order to do so the crosslinking agent reacts with the polyvinyl alcohol,

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BAD ORIQiNAL

be used. Such catalysts include magnesium chloride, zinc chloride, alum, ammonium chloride, Ammonium sulfate, salts of divalent and trivalent metals and acids, e.g. B. hydrochloric acid and acetic acid.

Suitable finely divided fillers used in accordance with the invention are naturally occurring Silicates, ζ. B. clay, kaolin, talc, bentonite sepiolite and mica, oxides such as ζ. Β. Titanium Dioxide, Zinc Oxide, Colloidal Silicon dioxide, diatomaceous earth silicon dioxide, carbonates, such as.ζ. Β. Calcium carbonate, magnesium carbonate, barium carbonate and sulphates, such as. B. barium sulfate and calcium sulfate.

The filler is preferably introduced into the hydrophilic layer in such a way, ζ. Β. by means of sand grinding, Ball milling or milling by means of vibrational energy, 'that the Size of the fillers has been reduced to less than 1 micron

fewer
is, and preferably / is 100 millimicrons.

The preferred fillers are silica, clay and Titanium dioxide. The preferred size of these fillers is in the range of 10 to 100 millimicrons. Preferably this is Ratio of filler to organic film-forming material in the layer from 0.5 to 10 of filler: 1 of organic film-forming material. Preferably both silica and clay are present, and most preferred when there is more clay than silica in the layer. In the

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Use of titanium dioxide as a filler. ■ the hydrophilic layer takes on a very white appearance. This helps to increase the contrast of the image and non-image areas after imaging the plate. Titanium dioxide cannot be used as a filler if a translucent plate is required; in this'% case, silica is the preferred filler.

The film material according to the invention can be used as a Direct image lithographic printing plate are used, d. H. an image can be applied directly to the plate using an oleophilic. Medium. An example of this type is typing an image onto a plate using typewriter tape attached to a Paint is impregnated on a grease base. Alternatively, the image can be applied to the plate using a colloidal | Transfer method, such as. B. Ektalith method, or an electrophotographic method, such as. B. the Xeroxography process, or a thermographic process be transmitted. . The colloidal transfer process is the transfer of an emulsion image of the kind as they are described in British patent specification 655 27 ^ 1st, understood to the film material according to the invention. The emulsion transferred is oleophilic and the plate can either

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after heat treatment or treatment with alkali can be colored in the usual way and is then ready for use as a lithographic plate. . · Under xeroxography, the application is more loaded

understood photoelectrically conductive selenium plate on the

with ..- .. ■■■■

^ after exposure / the original the image by means of cascade development of the plate with a thermoplastic powder is being developed. This resin image is transferred to the film material according to the invention, is heat-sealed and is then ready to use for coloring and use as a lithographic plate.

In another embodiment of the invention that can Silver material with a coating of a positive or negative acting photosensitive material are provided, what if it thus becomes a so-called presensitized lithographic * plate.

A negatively acting photosensitive material is understood to mean a material which is applied to the base layer that is sensitive to actinic light and that when exposed to actinic Light through a negative in the exposed areas undergoes a chemical reaction, which the exposed areas makes it insoluble and hydrophobic. The layer is developed by · dissolving the unexposed unchanged areas; leaving the insoluble areas that were left behind during staining

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forming a positive image of the original on the plate; the underlying hydrophilic base layer, which is revealed in this way, does not take on any color. The insoluble areas are either due to the fact that the drawn-up material is oleophilic, oleophilic or because the material becomes oleophilic _{on exposure to L 1 ClIt.} A large number Λ such photosensitive materials have been proposed and used. Examples of such materials are:

(A) Photosensitive polymers, such as. B. polyvinyl cinnamate, Polyvinyl phosphoric acid monoester of chalcones, styrene / maleic anhydride copolymers with a content of a cinnamoyl or chalcone radical, vinyl polymers with a Content of an azido group.

(b) Polymers together with a photosensitive compound that causes the polymer to be exposed hardens to light, such as B. gelatin and bichromate, gelatin and diazo compounds, polyacrylate and Diazo compounds, vinyl polymers and p-hydroxylbenzalacetophenone, Styrene / maleic anhydride copolymers and diazofluoborates.

(c) Photopolymerizable mixtures, such as. B. Acrylamide + NN'-methylene-bis-acrylamide in connection with a catalyst.

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(d) Polymeric diazonium compounds, such as ζ. B. that Condensate of 4-diazodiphenylamine and formaldehyde.

(e) Photosensitive compounds that can be applied directly to the carrier material,

without the addition of curable polymers, such as. B. Diazo compounds, diazostilbenes, naphthoquinonediazides, methylenefluorenesulfonic acid and cinnamoylfurfurylidene. These latter compounds are usually applied to the support together with a non-hardening resin such as e.g. B. a Novalak resin, drawn up in order to prevent them from crystallizing on the carrier. A common example of a negative-acting photosensitive layer of E is used according to the invention _r is 4-Diazodiphenylaminformaldehydharz.

A positive-acting photosensitive material is understood to mean a material that acts on the pillow material according to FIG Invention can be raised, which is sensitive to aotinic light and after 'exposure to actinic Light through a positive and after developing into the non-exposed areas an insoluble © leophiles positive Image results. ''

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. An example of such a positive acting material is a high molecular weight ester of diazooxydsulfonic acid which is insoluble in water and is photosensitive. When exposed to light, phenolic groups are generated which make the coating soluble in dilute aqueous alkali. After exposure, the exposed areas are dissolved away with an alkaline developer, wherein the original ester remains as an oleophilic image f that can be dyed in a conventional manner ..

When using the film material according to the invention either as a direct image plate or as the basis for a presensitized lithographic plate, the insolubilized, water-swellable organic film-forming polymeric material and the fillers create the hydrophilic background and the silica and other inorganic fillers, if they are present, an anchored i or toothed surface on · either the can firmly adhere directly labeled or transmitted oleophilic image or negative or positive-acting light-sensitive materials. The anchoring or interlocking also creates a container for the color in the picture areas and for the water in the non-picture areas, which makes it easier to work successfully on the plate.

109831/2195

The invention is explained in more detail below with the aid of examples.

example 1

Biaxially oriented polyethylene terephthalate film basecoat was coated as follows:

Coating 1 : A dilute solution of:

2,4-dichlorophenol 2.5 g

_ 2,4,6-trichlorophenol 2.5 g

Methanol x 100 ml

Dry for 90 seconds at 80 ° C.

Coating 2: A dilute solution of:

Vinylit VAGH 2.0 g

Carbon tetrachloride 80 ml

Acetone 20 ml -

Ethyl lactate ... 8 ml

Drying for 5 minutes

at 100 ° C.

Coating 3: A hydrophilic lacquer made of:

Aerosil TK8OO (silicon

dioxide) 13.8 g

Surfil B (China tone) 27.6 g

Tioxyd RCR3 (titanium dioxide) 26.2 g

Polyvinyl alcohol 11.0 g

Melamine formaldehyde 15.5 S

Magnesium chloride hexahydrate 2.9 S

Tergitol NP 35 (nieht-ioai-

cal wetting agent,) 0.1 g

Water 350 ml

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The above paint was sand milled for 10 minutes and then sufficient acetic acid was added to bring the pH between 4 and 4 .

After this lacquer had been coated, it was then dried at 110 ° C. for 10 minutes. The plate g thus prepared was then mounted in a typewriter, and a word image was typed on the plate using a fat-based paint. This plate was then placed on an offset printing press and 100 clear copies of the original were obtained. No sign of image disturbance was seen on the plate after use.

Example 2

After the coating had dried, the plate according to Example 1 was coated with the following solution | sensitized:

ZAL (a diazonium dipheny lamin / form-

aldehyde resin) 0.8 g

Water '30 ml

Methanol 70 ml

The plate thus sensitized was then dried at 70 ° C. for 5 minutes. After drying, it was exposed to actinic light through a photographic negative

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The plate was then developed and placed in an offset lithographic press. 1000 good positive copies of the original of the photographic negative were obtained. No evidence of image distortion was found on the plate to see the use.

Example 3

■ ■. ■ «

Polyester film base layer was coated as follows:

Coating 1: Vinylit VAGH 0.75.g

Acetone 9 ^ ml '2,4,6-triehlophenol 2.5 g 2,4-dichlorophenol 2.5 g

Methanol 5.0 ml

lytron 0.215 g

It was dried at 100 ° C. for 5 minutes.

Coating 2: lacquer coating like coating 3 in example 1.

It is evident that the coating 1 in this example is an example of the combination of the chlorophenol treatment (coating 1) with an interlayer bar (coating c according to example 1).

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179A012

Example 4

Polyester film base layer was coated as follows: ■ Coating 1: 3-methyl-4-chlorophenol 5.0 g methanol 100 ml

It was dried at 70 ° C. for 2 minutes.

Coating 2: A copolymer with a content of: 70 mol # vinyl monochloroacetate 29 mol # vinyl alcohol

1 mole of vinyl acetate 1.0 g Acetone 100 ml

coating

It was dried at 80 ° C. for 1 minute.

Paint coating as in the example

Example 5

Coating 1: trichloroacetic acid acetone

5 100

Saran F220 (a vinylidene chloride acrylonitrile copolymer)

It was for 5 minutes

G
ml

dried at 90 ° C. This is also an example of the union of coatings 1 and 2.

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Cover 2: Elvanol 50/42 12th S. Aerosil ΤΚδΟΟ 15th G Surfil B 30th ß Tioxid RCR ^ 28.5 S. Melamine formaldehyde
resin 12.5 S. Magnesium chloride
. hexahydrate 2.2 G Methanol 179 ml water 179 ml

The above-mentioned varnish was sand-ground for 10 minutes, and then a sufficiently large amount of hydrochloric acid became added to adjust the pH within the range between 4 and 5. After plating this The lacquer was then dried at 110 ° C. for 10 minutes.

Example 6

Polyester film base layer was coated as follows: Coating 1; 2,4-dichlorophenol 5 S 2,4,6-trichlorophenol 5 g Saran P220 2 g

Acetone 100 ml

It was for 5 minutes

dried at 105 ° C. .

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8th G 19th G 38 G 25th G 10 G 1, 8 g 110 ml 135 ml

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Coating 2: Elvanol 72/51 Aerosil ΤΚδΟΟ Surfil B Tioxid RCR3

BT309 (helamine forraaldehyde resin)

Magnesium chloride hexahydrate

Methanol

water

The above-mentioned varnish was sand-milled for 10 minutes, and then a sufficiently large amount was made Hydrochloric acid added to adjust the pH within the range between 4 and 5. After plating this The lacquer was then dried at 110 ° C. for 10 minutes.

Example 7

Polyester film base layer was coated with layers 1 and 2 as described in Example 1. 1

Coating 3i The following varnish was applied:

Klucel E (hydroxypropyl ethyl cellulose)

Surfil B Aerosil ΤΚδΟΟ Tioxid RCR3 Toluenesulfonic acid

Epok U 9190 (urea formaldehyde)

acetone
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23.2 G G 43.5 G ml 21.7 G 5.8 G 0.36 g 5.8 300

The varnish was coated and then it became during Dried for 20 minutes at 120 ° C.

Example 8

Biaxially oriented polyester film base layer was coated with layers 1 and 2 according to Example 1. Cover 3: The ' following!. ·. Varnish was applied;

Elvanol 72/51 6th G Aerosil TK8OO 25th G Melamine formaldehyde ■
resin 8th S. Magnesium chloride,
hexahydrate 1, ig •. Methanol 119 ml water 156 ml

The above-mentioned varnish became for 2 minutes

™ sand-milled and then a sufficient amount of hydrochloric acid was added added to adjust the pH within the range between 4 and 5. After covering the The paint was then dried at 120 ° C. for 10 minutes.

The plates prepared in Examples 3 to 8 can be used as either direct image lithographic plates or they can be sensitized as in Example 2 and used as * presensitized lithographic plates can be used or as plates that are imaged according to the ectalith or xeroxography process.

109831/2195

In the examples mentioned above, the following trade names were used.

Trade name name

Aerosil ΤΚδΌΟ 'BT5O9

Ectalith

Elvanol
Epok U9190 Klucel E.
Ly tr on
Saran F220 Surfil B
Tergitol NP? 5 Tloxid RCR? Vinyllt VAGH

Description Silicon dioxide manufacturer Degussa

Methylated melamine formaldehyde

Gelatin transfer process

Polyvinyl alcohol Melamine formaldehyde

Hydroxypropyl ethyl cellulose

Ethylene oxide polymer BIP
Chemicals Ltd.

Kodak Ltd.

DuPont Co., Ltd.

British Resin Products

Hercules Powder Co.

Union Carbide Chemicals Dept.

Vinylidene Chloride / Acrylic - Dow Chemical Nitrile Copolymer Co. Ltd.

Chinaton Scott Baths & Co. Ltd.

Non-ionic Wetting Union Carbide medium Ltd.

Rutile Titanium Dioxide British Titan Products Co. Ltd.

partially hydrolyzed Bakelite Ltd. Vinyl chloride / vinyl acetate copolymer

Diazonlumdiphenylamineform * ldehyde Pisons Industrial Chemicals

109831/2196 QRiQINAL

Claims (9)

V / 94U14 claims 1. 'Pi Immaterial, which can be converted into a lithographic printing plate comprising a substrate layer of polyester film material, said punch at least one surface of the polyester film material with a solution or dispersion in a volatile medium with at least one substance, such as halogen-containing phenolic Sub-W or chlorine-substituted aliphatic acids, have been treated at a temperature of at least 50 ° C is, according to patent (Pat. Anm. P 15 44 664.7), thereby characterized in that an intermediate layer adheres to the surface treated in this way, consisting of: (A) vinyl chloride-vinyl acetate-Misehpolyraerisat and partially hydrolyze vinyl chloride-vinyl lace tat - Copolymers, or (b) vinylidene chloride-acrylonitrile mixed polynförisate and t Copolymer of vinylidene chloride acrylic acid and methacrylic acid esters,. - ♦ or (c) Polyvinylhalogenacetaten and Misehpoljnoerisaten from Vinyl haloacetates,
. or (d) bienol formaldehyde-> urea formaldehyde and melamine formaldehyde resins, or (e) cellulose nitrate and cellulose acetate butyrate, or (f) Poljrraerisaten from Acryl- and MethaorylsÄupen and «•« tern, and Misohpolymerieat · these acidic and Iet «r with adverse vinylunesÄttiletWi monomers, - 23 - and that a hydrophilic layer which is a water-swellable organic layer is superimposed on the intermediate layer film-forming material which has been made insoluble and which contains at least one finely divided inorganic Contains filler. 2. Film material according to claim 1, characterized in that that the polyester film is polyethylene terephthalate film which has been biaxially oriented. 3. Film material according to claim 1 or 2, characterized in that that the water-swellable organic film-forming material cellulose ether, carboxymethyl cellulose, polyacrylamides, Polyvinylpyrrolidone, sodium alginate, natural rubber, Polyvinyl alcohols, carbohydrates, proteins, vinyl / maleic acid copolymers or ethylene oxide polymers. 4. Film material according to one of claims 1 to 3, | characterized in that the water-swellable organic film-forming material comprises a crosslinking agent. 5. film material according to claim 4, characterized in that the water-swellable organic film-forming material a Catalyst for the crosslinking reaction. 6. Film material according to one of claims 1 to 5, characterized in that the water-swellable organic film-forming material is polyvinyl acetate, which is up to one Extent of 84 to 98 # has been hydrolyzed. , 1A9831 / 2195 - 24 - 7. Film material according to claim β, characterized in that the hydrolyzed polyvinyl acetate methylated melamine-formaldehyde resin as a crosslinking agent. 8. Pilmmaterial according to one of claims 1 to 7, characterized in that the filler silicon dioxide, Is clay or titanium dioxide. ' 9. Film material according to one of claims 1 to 8, characterized in that on the hydrophilic layer a layer of a positive-working or negative-working photosensitive material is applied. ■, 4 * 109931/2195